Chlorinated sulfones



United States Patent 3,294,845 CHLOATED SULFONES Karoly Szabo, Orinda, Califi, assignor to Staufier Chemical Company, New York, N.Y., a corporation of Delaware No Drawing. Filed Get. 1, 1963, Ser. No. 312,864 6 Claims. (Cl. 260-607) The present application is a continuation-in-part of my copending application Serial Number 117,510, filed June 16, 1961, now US. Patent 3,106,585, issued October 8, 1963.

This invention is concerned with certain novel chlorinated sulfones. In particular, it is concerned with certain novel compounds having a formula selected from the group consisting of wherein R is selected from the group consisting of saturated and unsaturated linear alkyl groups, saturated and unsaturated chlorinated linear alkyl groups and arylalkyl groups, and R is selected from the group consisting of saturated and unsaturated linear alkyl groups, saturated and unsaturated chlorinated linear alkyl groups, aryalkyl groups, aryl groups, chlorinated aryl groups, nitrated aryl groups, and cyclohexyl.

The novel compounds of the present invention are prepared by reacting a trichloromethylsulfone with a phosphite ester containing at least one alkoxy group linked to the phosphorus. For the compounds having the first formula above, the reaction may be represented by the following equation:

RIIIO wherein R and R have the meaning given above and wherein R and R and preferably the same as R. The compounds having the second formula given above are prepared according to the following equation:

wherein R, R" and R are as defined above.

(CH =CHCH CCl 80 is useful as a fungicide, and the compound is useful as an insecticide. Unsaturated compounds of the present invention may be used as monomers in polymers or copolymers and impart flame resistance due to the presence of the halogen. A certain amount of im- 3,294,845 Patented Dec. 27, 1966 "ice pact resistance is also imparted to polymers and copolymers by these compounds, apparently by the sulfone grouping. An example for such useful monomer is the compound CH =CHCH CCl SO CH BL The compound CH =CHCH CCl SO CH CH COOH may be incorporated into polymers with other unsaturated monomers Where its polar carboxylic acid group enhances the dyeability of the resulting polymer. In addition, the compounds of the present invention are valuable as intermediates for the syntheses of still other compounds.

The reaction takes place exothermicly, and is spontane ous, although it is sometimes advantageous to use slightly elevated temperatures. The reaction is most conveniently carried out in an inert solvent, preferably a hydrocarbon such as benzene.

The only requirements for the reaction are that the phosphite ester contain at least one alkoxy group bonded to the phosphorus, and that the other reactant be a trichloromethylsulfone. The presence or absence of substitutients on portions of eithermolecule removed from the site of reaction is of no consequence. In cases where the phosphite ester contains a free amine substitutient, the yield may sometimes be somewhat reduced by a side reaction with the halogen of the trichloromethyl sulfone, but in any case the desired reaction will take place, and a new carbon to carbon bond will be formed to produce an a,a-dichlorosulfone. It is a particular advantage that the reaction proceeds under gentle conditions and that it can be applied to the synthesis of functionally substituted and/ or unsaturated sulfones without interferring with the unsaturation or the functional substitutient.

The following examples are given solely for the purpose of illustration and are not to be construed as limitations on the present invention, many variations of which Will occur to those skilled in the art without departing from the spirit or scope of the invention.

EXAMPLE 1 p-Chlorophenyl-(1,1-dichl0ro-3-methyl 3 butenyl)-sulf0ne The p-chlorophenyl-trichloromethyl sulf-one (19.6 g.) is dissolved in benzene (60 ml.) at 65 C. and the trimethallyl phosphite (2 0 g.) is added at once. The exothermic reaction, which raises the temperature up to 88 C., seems to be retarded for a few minutes. When the temperature of the reaction mixture starts dropping, it is taken that the reaction has been completed. The solvent is stripped off at reduced pressure and the oily residue is filtered by suction.

The separation of dimethallyl-phosphorochloridate, the byproduct of the reaction, is attempted by distillation at reduced pressure, 8.5 ml. (9 g., 60% yield of the theoretical) of this by-product has been obtained, B.P. 96-8" C., N =1,4571.

The main product crystallizes when cooled down to give 16 g. of a white solid. Yield 78% of the theory. The M.P. of the product is 100 C. after recrystallization (methanol).

N-octy-l-trichloromethyl-sulfone (3.3 g.) and benzene (40 ml.) are placed in an open beaker and trimethallylphosphite (3.2 g.) is added at once. The temperature of the mixture rises from 24 to 32 C., then the mixture starts cooling.

The solvent is stripped off and the oily product is recrystallized from abs. alcohol to obtain a white solid with a The reagents, icyclohexyl-trichloromethyl-sulfone (6.6

.g.), trimethallyl phosphite (6 .5 g.) and benzene (40 ml.) .are brought together in an Erlenmeyer flask at room temperature. The reaction, if any, is very moderate at this temperature. Therefore, in order to complete the reaction the mixture is warmed up to 80 C. on a hot plate, then allowed to cool down.

The benzene is removed in vacuum and the oil residue is crystallized from abs. alcohol to obtain 3 g. (42% yield of the theory) of a white solid melting at 54 C.

EXAMPLE 5 I p-Nitrophenyl- (1,1 -dz'ch l0r0-3-mcthyl-3-butenyl) -sulfone I This preparation was carried out in a fashion similar to Example 1, and the product, a slightly yellow solid, is obtained in a yield of 83.5%. The pure product, recrystallized from methanol and hexane, melts at 116 C.

EXAMPLE 6 4-chlorophenyl- (1,1 -dichl0r0ethyl) -sul 0ne The mixture of p-chlorophenyl-trichloromethyl-sulfone (29.4 'g.) and benzene (50 m1.) is warmed up to 65 C. and trimeth-ylphosphite (12.4 g.) is added in small portions. A spontaneous, slightly exothermic reaction takes place. When the addition is completed the reaction mixture is allowed to cool down to room temperature and worked up as in Example 1, to obtain .a colorless crystal mass of 28 g. (100% yield). The product is purified by recrystallizations from abs. alcohol to obtain a White solid melting at 110 C.

The other reaction product, dimethylphosphorochloridate, has been identified as its anilide (M.P. 89 C.).

EXAMPLE 7 Lauryl- 1,1 -dich loroethyl -sul fone Trimethy-lphosphite (3 g.) is added at once to the mixture of lauryl-trichloromethyl-sulfone (7 g.) and benzene (20 ml). A slightly exothermic reaction takes place which is completed by heating the mixture to reflux for 20 minutes; then the solvent is removed at reduced pressure.

The residue is taken up in ml. of methanol and the recrystallization is attempted applying Dry-Ice bath temperatures. The product precipitates in White flakes, which melt at 24 C. Yield is 3.5 g., 54% of the theory.

EXAMPLE 8 Ch lorometizyl- (1 ,1 dichloropropyl -sulf0ne ClCI-I SO CCl CH CH Triethylphosphite (8.5 g., 0.053 M) is added to the mixture of chloromethyl-trichloromethyl-sulfone 1 1.6 g, 0.05 M) and hexane (50 ml). The reaction is spontaneous, bringing the temperature of the mixture up to 62 C. When the temperature starts dropping, it is taken as the completion of the reaction.

The solvent is removed on reduced pressure and 7 ml. of diethylphosphorochloridate is also separated by distillation in vacuo.

The residue is considered to be the crude product. It could not be crystallized even at Dry-Ice temperature. Yield is 9.5 g., 84% of the theory N =1;4904.

The pure compound is obtained by distillation. BR 1.5 mm. is 96 C., N =1.4934.

Chloromethyl-trichloromethyl-sulfone (11.6 g.) hexane (60 ml.) and trirnethallylphosphite are brought together in an Erlenmeyer flask. A moderately exothermic reaction takes place raising the temperature of the mixture (18 C.) to 32 C. When the temperature stops rising the mixture is heated up to 60 C. and kept there for 10 minutes.

After removing the solvent 9 ml. of dimetha-llyl phosphorochloridate is obtained by distillation at 2.5 mm. between 10610 C.

The residue Weighs 10.5 g. (yield 84%). It is a slightly yellow oil with a R.I. of 1.4949. The pure product distills at 119 C. at 2 mm. pressure having a refractive index of 1.4988.

EXAMPLE 10 Chloromethyl- (1,1-dichlor0ethyl) -sulf0ne ClCH SO CCl CH EXAMPLE 1 1 Phenyl- (1,1 -dichl0r0-3-methyl-B-butentyl) -sud.'gone It has been prepared in a yield of 53% by the method described in Example 1. The product melts at 623 C.

EXAMPLE 12 P-Nitrophenyl- (1,1 -aich10r0ethyl) -sulf0ne Nos-4020 012011 This compound has been prepared as described in Example 5 and obtained in a yield 91%. It is characterized by a M.P. of 156 C.

EXAMPLE 13 p-Chlorophenyl-(1,1-dichlor0-3-butenyl) sulfa e This compound has been prepared by the method given in Example 1. It has been obtained in a yield of 60% in a form of a white solid which melts after several recrystallizations at 66 C.

EXAMPLE 14 Preparation a,oz,a',a-tetrachlorodiethylsulfone CH -CCl SO CCl CH 15 g. of hexachlorodimethylsulfone is dissolved in 50 m1. of benzene at room temperature. 13 g. of trimethylphosphite is added to this mixture in small portions. The reaction is vigorous and exothermic and the temperature quickly arises up to the boiling point of the solvent (80 C.). To moderate the reaction, the reaction flask is placed in a cold water bath and the mixture is allowed to cool down to 40 C. after each addition. (This is helped by shaking the reaction flask.)

The addition is completed in 20 minutes; then the solvent is stripped off to obtain 17 g. of a pale yellow oily product. A sample of the product is mixed with acetone, then precipitated by adding water. On shaking, the precipitate solidifies to a colorless solid which melts at 49-51 C. The whole batch is worked up this Way to obtain 12 g. of product.

It is recrystallized from abs. EtOI-I at Dry-Ice temperature to obtain the pure product melting at 567 C.

Mixed M.P. of the product with an authentic sample of a,a,a,a-tetrachlorodiethylsulfone does not shown depression.

EXAMPLE 15 a,a,u',a'-Tetrachlorodipropylsulfone Hexachlorodimethylsulfone (15 g.) is dissolved in 50 ml. benzene. A mixture of triethylphosphite (25 g.) and benzene (40 ml.) is added portionwise to the above solution. To moderate the reaction, a cold water bath is applied. The temperature is maintained below 40 C.

The addition is completed in minutes and the solvent is stripped off on reduced pressure. A fraction (9 ml.) following the benzene fraction and boiling at 62 C. at 3 mm. has been separated and identified as diethylphosphonochloridate.

The residue, a light yellow oil is taken up in abs. alcohol and recrystallized with Dry Ice cooling. M.P. 46 0., yield 11 .g.

EXAMPLE 16 Hexachlorodimethylsulfone (45 g.) is dissolved in 100 ml. of benzene and triallylphosphite (60.6 g.) is added portionwise while maintaining the temperature of the reaction mixture below C. with the aid of a cold water bath.

The solvent is stripped oh and the separation of diallylphosphonochloridate is achieved by high vacuum distillation.

33 ml. of diallyl-phosphonochloridate is collected. It distills at 0.3-0.5 mm. pressure at 83-7" C. Yield 39 g., 67%. N =1.4529.

The residue is kept refrigerated overnight. Next morning, a colorless crystal mass is obtained, which after recrystallization melts at C. Yield 39.7 g. (theory 46.8 g.).

EXAMPLE 17 By procedures analogous to those of the foregoing examples, other trichloromethylsulfones may be reacted with other phosphite esters containing an alkoxy group on the phosphorus atom. In all cases, an u,a-dichlorosulfone is obtained in a fashion similar to that in the other examples, i.e. by replacement of one of the halogens by an alkyl group.

What is claimed is:

1. Compounds having the formula wherein R is selected from the group consisting of alkyl and alkenyl, and R is selected from the group consisting of alkyLchIoroalkyl, chloroalkenyl, cyclohexyl, phenyl, nitrophenyl and chlorophenyl.

2. The compound according to claim 1, wherein R is 2-methyl-2-propeny1 and R is p-chlorophenyl.

3. The compound according to claim 1, wherein R is ethyl and R is chloromethyl.

4. The compound according to claim 1, wherein R is ethyl and R is 1,1-dichloropropyl.

5. The compound according to claim 1, wherein R is 2-rnethyl-2-propenyl and R is cyclohexyl.

6. Bis-(1,1-dichloro-3,4 butenyl)-sulfone.

References Cited by the Examiner UNITED STATES PATENTS 3,106,585 10/1965 Szabo 260-607 CHARLES B. PARKER, Primary Examiner,

D. R. PHILLIPS, Assistant Examiner, 

1. COMPOUNDS HAVING THE FORMULA 